Supersensitization of photographic emulsions using triazines



U ited States Patent s s l 1 2,875,058 SUPERSENSITIZATION F PHOTOGRAPHICEMULSIONS USING TRIAZINES Burt H. Carroll and Jean E. Jones, Rochester,N ..Y., assignors to Eastman Kodak Company, Rochester, N. Y., acorporation of New Jersey Application October 12, 1955, Serial No.540,053

17 Claims. (Cl. 96-104) This invention relates to photographic silverhalide emulsions containing certain cyanine dyes, and assupersensitizers therefor, bis-triazinylaminostilbene compounds.

It is known in the art of making photographic emulsions that certaindyes ofthe cyanine class alter the sensitivity of photographic emulsionsof the gelatino-silver-halide kind, when the dyes are incorporated inthe emulsions. It is also known that the sensitization produced by agiven dye varies somewhat with the type of emulsion in which the dye isincorporated. Furthermore, the sensitization of a given emulsion by agiven dye may bealtered by varying the conditions in the emulsion. Forexample,

the sensitization may be increased by increasingthe silver ionconcentration or decreasing the hydrogen ion concentration (i, e.,increasing the alkalinity) or both. Thus, sensitization can beincreased'by bathing plates, coated with aspectrally sensitizedemulsion, in water or in aqueous solutions of ammonia. Such a process ofaltering the sensitivity ofa sensitized emulsion by increasing thesilver ion concentration and/or bydecreasing the hydrogen ionconcentration is commonly called hypersensitization. Hypersensitizedemulsions have generally poor keeping qualities. i

We have now found another means ofaltering the sensitivity in emulsionscontaining certain cyanine dyes. Since the conditions in theemulsion, i.e., the hydrogen ion and/or the silver ion concentration undergo littleor no change in our method, we shall designate our method as a kind ofsupersensitization.

Itis, therefore, an object of our invention to provide photographicemulsions containing certain cyanine dyes and, as supersensitizerstherefor, bis-triazinylaminostilbene compounds. Anotherobject is toprovide a process for preparing these supersensitized"emulsions. Stillanother object is to provide photographic emulsions containing certaincyanine dyes F and bis triazinylaminostilbene compounds, which are.especiallyuseful in color photography. Other objects will becomeapparent from a consideration, of the following description andexamples.

The cyanine dyes which are useful inpracticing our invention, canadvantageously he represented. by? the following general formula: r r

2,875,058 Patented Feb. 24, a

i and R each represents a hydrogen atom or a methyl benzothiazole,S-ethoxybenzothiazole, 5,6-dimethylbenzogroup, X represents an acidradical (e g., chloride, bromide, iodide, perchlorate, thiocyanate,p-toluenesulfonate, benzenesulfonate, methylsulfate, ethylsulfate, etc.)d represents a positive integer of from 1 to 3, n represents a positiveinteger of from 1 to 2, Z represents the nonmetallic atoms necessary tocomplete a heterocyclic nucleus of the benzothiazole series (e; g.,benzothiazole, 4-chlorobenzothiazole, 5-chlorobenzothiazole,6-chlorobenzothiazole, 7-chlorobenzothiazole, 4-methylbenzothiazole,.S-methylbenzothiazole, 6-methylbenzothiazole, S-broniobenzothiazole,6-bromobenzothiazole,' 4-phenyl benzothiazole, 5 -phenylbenzothiazole,4-methoxybenzo thiazole, S-methoxybenzothiazole, G-methoxybenzothrazoleS-iodobenzothiazole, fi-iodobenzothiazole, 4-ethoxythiazole, 5-hydroxyben'zothiazo1e, 6-hydroxybenzothiazole, etc.), or a heterocyclicnucleus of the naphthothiazole series (e. g., ot-naphthothiazole,fl-naphthothiazole, 7- methoxy-a-naphthothiazole,8-methoxy-a-naphthothiazole, S-methoxy-fl-naphthothiazole,5-ethoxy-a-naphthothiazole, etc.), and Z represents the non-metallicatoms necessary to complete a heterocyclic nucleus containing from 5 (nis 1) to 6 (n is 2) atoms in the heterocyclic ring, such as aheterocyclic nucleus of the benzothiazole series (e. g., those nucleilisted under'Z above), a heterocyclic nucleus of the naphthothiazoleseries (e. g., under Z above), a heterocyclic nucleus of thebenzoselenazole series (e. g., benzoselenazole, S-chlorobenzoselenazole, 6-methoxybenzoselenazole, S-methoxybenzoselenazole, etc.),

wherein R and R, each represents analk yl g., methyl,ethy1',;8-hydroxyethy1; carboxymethyl, p carboxybenzimidazole series (e.g., benzimidazole, 5,6 dichlorobenziidazole, 1,7-trimethyla heterocyclicnucleus of the naphthoselenazole series (e. g., a-naphthoselenazole,,B-naphthoselenazole, etc.), a heterocyclic nucleus of the benzoxazoleseries (e. g., benzoxazole, 5-hydroxybenzoxazole, 6-hydroxybenzoxazole,S-chlorobenzoxazole, 5- methoxybenzoxazole, 6-methoxybenzoxazole,S-phenylbenzoxazole, 5;bromobenzoxazole, etc.), and a heterocyclicnucleus of the naphthoxaz ole series (e. g., anaphthoxazole,fi-naphthoxazole, etc.), a heterocyclic nucleus of the Z-quinolineseries (e. g., methyl 2 quinoline, 7-methyl-2-quinoline, 8-methyl-2-quinoline, 6-chloro-2-quinoline, 8-chloro-2-quinoline, 4-

chloro 2 quinoline, S-ethoxy-Z-quinoline, 6ethoxy-2- quinoline,7-ethoxy-2-quinoline, 6-hydroxy-2-quinoline, 7- hydroxy-Z-quinoline,6-methoxy-2-quinoline, etc.) a heterocyclic nucleus of the 4-quin0lincseries (e. g., 4- quinoline, 6-methoxy-4-quinoline,7-methyl-4-quinoline, 8-methy1-4-quinoline, etc.), a heterocyclicnucleus of the benz imidazole, 5-chloro-- those nuclei listedZ-quinoline, 6-

enebenzimidiazole, etc.), and a heterocyclic nucleus of N 21:: )5,6benzoqulnollne series (e. g., 5,6 benzo 2 qumolme, i NW Q G X w Thebis-triazinylaminostilbene compounds useful in N practicing ourinvention have been previously employed 5 y in the art as fluorescentagents and as bleaching (optical) NH agents, and hence are widely knownsubstances. Especially useful compounds of this class comprise thosecompounds represented by the following general formula:

n Y N 411m -mm f \T NH F m (1H2 1 N ma L 3; 5 r R1 7 Rs V $0311 sonswherein R R R and R each represents a hydrogen I I I atom, or asubstituent group, such as hydroxyl, aryloxyl 4,4 -b1S{4-[4 Y N y a l-(.e. g., phenoxyl, o-toloxyl, p-sulfophenoxyl, etc.), .alkoxyl q Y- -Y2,2 (e. g., methoxyl, ethoxyl, etc.), a halogen atom (e. g., o c acldchlor1ne, brom 1ne, etc.), a hBtCIOCYCIIC radical (e. g., 4,4 bis[4 (4sulfoanilino) 6 I8 hydroxyethylamino morpholmyl plpendyl an alkylthlogroup s-triazin-Z-ylamino]stilbene-2 2-disulfonic acid if gzi i f gg anfig fi p 5. 4,4-bis[4,6-dianilino-s-triazinyl-i ylaminolstilbenep eny1o, 0 y 10, e c. a erocyc y 10 gr p 22, disulf0nic acid (e. g.,benzothiazylthio, etc.), an amino group, an alkyl- 1 amino group (6. g.,methylamino, ethylamino, propyl- 3O -P y-6-(fi-hydroxyethylamino) s-tr1- amino, dimethylarnino, diethylamino, dodecyl amino, cy- F f QQ P fclohexylamino, p-hydroxyethylamino, di-fi-hydroxyethyl- 4,4 E f amino,gsulfoethylamino, etc.), an arylamino group 8.4,4-b1s(4,6-d1hydroxy-s-tr1azm-2 ylam1no)st1lbene- (e. g., anilino, 0-,m-, and'p-sulfoanilino, o-, m-, and 2,2"diSu1fm1i7 acid y Yp-chloroanilino, o-, m-, and p-anisylamino, o-, m d 9.4,4-bis(4-anilino-6-hydroxy -s-triazin-2 ylamino)stilp-toludino, o-, m-,and p-carboxyanilino, hydroxyanilino, bene-2,2'-disulfonic acidsulfonaphthylamiuo, o-, m-, and p-aminoanilino, p-acet- 10.4,4'-bis[4-(2-chloroanilino)-6-hydroxy s -triaZi11-2- amidoanilino,etc.), etc.,' and R and R each represents 7 ylamino] ti1bene-2,2'-disu1fmi id a hydrogen atom a Wat6T'S1ubi1 iZing group, Such as 11.4,4'-bis[4-(5-sulfonaphthylamino)-6-hydroxy-s trisulfo, carboxyl, etc.-(as well as alkall metal or amine salts 40 2 1 i ti1b 2 2' di 1f i acidof such groups). Many of the compounds represented by 2 4 4 4 1 i [3- 1fthy1 i Formula I b are known Substances, and methodstriazin-Z-ylamino]stilbene-2,2'-disulfonic acid for preparing thesecompounds are'well known. Listed 13. 4 4-, bis[4 N morpholinyl 6 (4,Su1foanflino) S below are representative compounds selected from thoseazin z ylamino]stilbene z zudisulfonic acid represented by Formula II,although our invention is not 14 4 6 di(N mor holin 1 mino] limited inany sense to these particular compounds. f 2 7 y a While the structuralformulas are included for only the 6116' omaacl first three compounds,it is to be understood that the same P x 'PYIaZOhP numbering system isemployed throughout the specifica- 1 01- YQ Y w: Ylannno}st11' tion. a Ybene-2,2'-drsulfon1c acid, v i v 16. 4-[4-ethylamino-6-diQ3hydroxyethyllamino s tri- 1 1 azin-2-y1amino]-4'-[4-methylamino 6 (flhy- N N\ I droxyethylamino)-s-triazin-2 ylaminolstilbene- 1 W' 'Q2,2-disulfonic acid I H I H N N 17. .4-[4'-methy1amino-6-(phydroixyethylamino) s tri- 3 v a \K V azin-2-ylamino]-4-[4-ethylamino 6(2 anisi- NE NH 1 'dino) -s-triazin-2-y1amino]stilbene-2,2' disulfonic le l acid G0 18. 4-[4-ethylamino-6-(fl-hydroxyethylamino)-s triazin- 2ylamino] 4' [4,6 diamino-s-triazin 2 yl- S I 2 3amino]stilbene-2,2-disulfonic acid 19.4-4'-bis[4-chloro-6-di(,B-hydroxyethyl) amino s tri- 4,4-bis [4-3'-sulfoanilino) -6-amino-s-triazin-2- azin-2-ylamino]stilbene-2,2'-disulfonic acid ylamino]-stilbene-2,2'-disulfonic acidS0311 S0313 IH-CHzCHa-OH I TH-CH2CHr-OH1,4'-bis[4,6-di(}3-hydroxyethylamino)-s-triazin-2- 20. 4,4'- bis[4y-anilino-6-(p :hydroxyethylamino) 7 stri-.ylarnino]-stilbene-2,2'-disulfonic acid azin-Z-yl'amino]stilbene-2,2-disulionicy acid triazin-Z-ylamino]stilbene-2,2'-disulfonic acid 26.

acid 27.

bene-2,2-disulfonic acid 28.

azin-Z-ylamino)stilbene-2,2'-disulfonic acid Compounds of the above typewhich can advantageously be employed in practicing our invention havebeen described in one or more sentative patents:

United States:

2,171,427, Aug. 29, 1939 2,473,475, June 14, 1949 2,595,030, Apr. 29,1952 2,660,578, Nov. 24, 1953 British:

595,065, Nov. 26, 1947 623,849, May 24, 1949 624,051, May 26, 1949624,052, May 26, 1949 678,291, Sept. 3, 195,2 681,642, Oct. 29, 1952 it705,406, Mar. .10, 1954 These products have been previously employed inthe textile field, and are sold under such trade names as Leucophor B,Calcofluor White MR, Tinopal (SP, WR, BV277, 2B, GS, NG), Blancofor SC,Hiltamine (BSP, N, 801., GT6), and the like.

The dyes represented by Formula I above can advantageously be preparedas described in the copending application of D. W. Heseltine, Serial No.400,810, filed December 28, 1953 (now U. S. Patent 2,734,900, issuedFeb. 14, 1956), and also British Patent 595,784.

According to our invention, we incorporate one or more of the cyaninedyes represented by Formula I above with one or mores-triazinylaminostilbene compounds, such as those represented by FormulaII above. Our invention is particularly directed to the ordinarilyemployed gelatino-silver-halide emulsions. ,.However, oursupersensitizing combinations can be employed in silver halide emulsionsin which the. carrier is other than gelatin, e. g., a resinous substanceor cellulosic material which has no deteriorating elfect on the lightofthe following reprej "tions. 4,4-bis[4-phenyltl1io-6-(;8hydroxyethylamino) s- 4,4'-bis(s-triazin-Z-ylamino)stilbene 2,2disulfonic 4,4-bis(4-hydroxy-6-amino-s-triazin-2 ylamino)stil- #1:

' 111 can also be used. The cyanine 4,4-bis(4-chloro-6trimethylolmethylamino s trisensitive materials. The cyanine dyes ands-triazinyl-.

aminostilbene compounds can be employed in various concentrationsdepending upon the effects desired.

Ordinarily, the optimum or near optimum concentration of the cyaninedyes which we employ in prac-. ticing our invention is of the order offrom 0.010 to 0.30

g. per mol. .of silver halide in the emulsion.

The s-triazinylaminostilbene compounds which we employ in our inventioncan advantageously be employed at a concentration of from about 0.03 to10.0 g. per mol.

of silver halide in the emulsion,

In general, the ratio of concentration of cyanine dye tos-triazinylaminostilbene compound can vary rather widely in ourcombinations, e. g., from 1:1 to 1:300 (by weight) in many cases.

The methods of incorporating sensitizing dyes in silver halide emulsionsare well known to those skilled in the art. The s-triazinylaminostilbenecompounds can be directly dispersed in the emulsions, or they can bedissolved in water (or an organic solvent, such as methanol, ethanol,etc., where the water-solubility is not sulficiently great) and added inthe form of their solu- While the cyanine dyes can be directly dispersedin the emulsions, it is convenient to add the same in the form ofsolutions in appropriate solvents. Methanol, ethanol, pyridine, and thelike have proven satisfactory for many of the dyes of Formula I.Mixtures of solvents, e. g., pyridine diluted with methanol or acetone,

dyes and s-triazinylaminostilbene compounds are dispersed in thefinished emulsions and should be uniformly distributed throughout theemulsions. The following procedure is satisfactory: Stock solutions ofthe cyanine dyes and stilbene compounds are prepared by dissolving thesame in appropriate solvents as described above.

Then, to the flowable gelatino-silver-halide emulsion, the desiredamounts of the stock solution of one of the dyes (or stilbene compounds)are slowly added, while stirring the emulsion. Stirring is continueduntil the dye is thoroughly incorporated in the emulsion. Then thedesired amount of the stock solution of the stilbene compound (or dye,if stilbene compound has been added first) is slowly added to theemulsion, while stirring. Stirring is continued until the secondsolution is thoroughly incorporated. The supersensitized emulsion canthen be coated out on a suitable support, such as glass, cellulosederivative film, resin film or paper, to a suitable thickness andallowed to dry. The details of such coating methods are well known tothose skilled in the art. The foregoingprocedures and proportions are tobe regarded only. as illustrative. Clearly, our invention is directed toanysilver halide emulsion containing a combination of the aforesaidcyanine dyes and s-triazinylaminostilbene compounds whereby asupersensitizing effect is obtained.

The following examples will serve to illustrate further the manner ofpracticing our invention.

In Table I below, to diflerent portions of the same batch ofphotographic gelatino-silver-halide emulsion were added (1) a cyaninedye, such as those represented by Formula I above, and (2) a combinationof the cyanine dye and a bis(s-triazin-2-ylamino) stilbene (in neutralaqueous solution). Then the emulsions were held at about 40 C. for ashort time and coated on a support, chill set, and dried. After exposurethrough a Wratten No. 25 filter, i. e., a filter which transmits:substantially no light of wavelength shorter than about 580 m i, in anEastman type IB sensitometer, the film strips were proc: essed for 3minutes in a developer Water to make 1 liter.

The speed (red), gamma and, fog for each. of the coat ingswas thenmeasured. The results are recorded i Table I. j H

' ical sensitizers, e. g., sulfur sensitizers (e. g., allyl thio- TABLEI Red Light Exposure Exam 1e Addenda and D e .mol. A X

p y (g/ g 30/E Gamma Fog Speed (a) 3,3 -diethyl 9 11 neopentylene6,7,6,7 dibenzothiadicarboeya- 36 4. 1 05 1 nine iodide (.075

(b) dye (a) (.075) plus Calcofiuor White MR 1 (.13) 76 3.1 .06 2 3,3-diethyl 9,11 neopentylenethiatetracarbocyanme iodide (.010)- 20 2. 6 04(d) dye (c) (.010) plus compound 4 (3.0) .30 2.5 .05 3 {(e)3,3-diethyl-9,11-neopentylenethiadicarbocyanine iodide (.0375). 56 3.1.06 (I) dye (e) (.0375) plus compound 6 (2.5)-... 117 2.4 .06 (g)3,3-diethyl- 9,11 neopentylene 6,7,6,7- dibenzothiatricarbo- .40 3.5 .054 cyanine iodide (.0375).

Eh) dye (g) (.0375) plus compound 6 (2.5) 1.47 3.3 .09 5 2') 3,3-diethyl-9,11-neopentylenethiatriearboeyanine iodide (.0376) .57 3. 3.05 (j) dye (i) (.0375) plus compoundfi (2.5)--.... 1.95 2.5 .06 G {(Ic)dye (c) (.018) .32 3.2 .13 (Z) dye (c) (.018) plus compound 6 (2 5) .542. 4 .34 7 ('m) dye (e) (.050) 13. 7 2.4 .05 (n) dye (e) (.050) plusCale 34.5 2.6 .05 8 {(0) dye (c) (.010) .22 2.7 .05 (p) dye (c) (.010)plus Calcofluor White MR 1 (3.0)- .70 2.1 .09 9 {(11) dye (e) (.075) 223.4 .06 "f" (r) dye (e) (.075) plus Calcofluor White MR 1 (2 122 2.8 .0510 {(8) dye (1') (.0375) 1.09 1.1 .05 (t) dye (2') (.0375) plusCalcofiuor White MR 1 19. 5 2. 6 .18 11 {(u) dye (c) (.018). m1 ml .13(v) dye (c) (.018) plus Oalcofluor White MR 1 (2.3) 6.15 2.2 .87 12 (w)dye (g) 1.02 1.0 .05 (I) dye (g) (.0375) plus Calcofiuor White MR(2.3).-... 5.1 3- 2 1 Calcofluor White MB is abis(s-triaziu-2'ylamino)stilbene-2,2-disulfonic acid (sodium salt).

In theabove table, the coatings of Example 1 were made from the samebatch of gelatino-silver-chlorobromide emulsion, the coatings of Example2 were made from the same batch of gelatino-silver bromiodide emulsion,the coatings of Examples 3, 4, 5 and 6 were made from the same batch ofgelatino-silver-chlorobromidc emulsion, the coatings of Examples 7 and 8were made from the same batch of gelatino-silver-bromiodide emul sion,and the coatings of Examples 9, l0, 11,"and 12 were made from the samebatch of gelatino-silver-chlorobromide emulsion.

'No measurements for the bis(s-triazin-2-ylamino)stilbene compoundsalone are given, since these compounds have no senistizing effect on theemulsions employed when used alone. Our invention is primarily directedto the ordinarily employed gelatino-silver-halide developing-outemulsions, e. g., gelatinorsilver-chloride, -chlorobromide,-chloroiodide, -chlorobrorniodide, -bromide and -bromiodidedeveloping-out emulsions. Emulsions which form the latent image mostlyinside the silver halide grains, such as theemulsions set forth in U. S.Patent 2,456,956, dated December 21, 1948, can also be employed inpracticing our invention.

The emulsions prepared in accordance with our invention can be coated inthe usual manner on any suitable support, e. g., glass, cellulosenitrate film, cellulose acetate film, polyvinylacetal resin film, paperor metal.

Photographic silver halide emulsions, such' as those listed above,containing the supersensitizing combinations of our invention can alsocontain such addenda as chemcarbamide, thiourea, allylisothiocyanate,cystine, etc.'),-

various gold compounds (e. g., potassium chloroaurate,

auric trichloride, etc.) (see U. S. latents 2,540,085; 2,597,856 and2,597,915), various palladium compounds, such as palladium chloride (U.S. 2,540,086), potassium chloropalladate (U. S. 2,598,079), etc., ormixtures of such sensitizers; antifo'ggants, such as ammoniumchloroplatinate' (U. S. 2,566,245), ammoniumv chloroplatinite (U. S.2,566,263), benzotriazole, nitrobenzimidazole, S-nitroindazole,benzidine, mercaptans, etc. (see Mees, The Theory of the PhotographicProcess, Macmillan Pub., page 460), or mixtures thereof; hardeners, suchas formaldehyde(-U. S. 1,763,533), chrome alum (U. S. 1',763,'533),'glyoxa'l (U. S. 1,870,354), dibromacrolein (British 406,750), etc;color couplers, such as those described in U. S. Patent 2,423,730;Spence and Carroll U. S. Patent 2,640,776, etc; or mixtures of suchaddenda. Dispersing agents for col-or couplers, such as those set forthin U. S. Patents 2,322,027 and 2,304,940, can also be employed in theabove-described emulsions.

Such silver halide emulsions can also contain thiazolidoues or otherultraviolet absorbing compounds, such as those described in thecopending application Serial No. 419,239, filed March 29, 1954, in thename of G. W. Sawdey, now U. S. Patent 2,739,888, issued March 27, 1956.While certain emulsion addenda, such as certain ultraviolet compounds,and certain color-forming compounds cause tie-sensitization orun-sensitizing eifects, it has been found that the new combinations ofour invention largely overcome such effects. Typical colorformingcompounds Which can be so employed include those in U. S. Patent2,322,027 and the following;

Coupler 1. l-hydroxy-Z- [6-(2',4'-di-tert. amylphenoxy) -n-butyl]naphthamide (U. S. Patent 2,474,293)

2. 1-hydroxy-4-phenylazo-4' (p tert. butylphenoxy- Z-naphthanilide (U.S. Patent 2,521,908)

3. 2-(2,4-di-tert. amylphenoxyacetamino)-4,6-dichloro-' S-methyl phenol(Graham U. S. application Serial No. 285,544, W U. S. Patent 2,725,291)

4. 2-(a2,4-di-tert. amylphenoxy-n butyrylamino) 5 4,6

dichloro-S-methyl phenol 5. 6-{a-{4-[u-(2,4-di-tert.amylphenoxy)butyramidolphenoxy}acetamido}-2,4-dichloro-3-methyl phenol6. 2 [3-(2",4- diamylphenoxy) acetamido] benzarnido-4-chloro-5-methylphenol 7. l-(2,4,6-trichlorophenyl) 3 [3-(2"',4-di-tert.

amylphenoxyacetamido) -benzamidol -5-pyrazolone (U. S. Patent 2,600,788)8. 1-(2,4,6-trichloropheny1) 3 [3--(2",4'-di-tert.-

amylphenoxyacetamido)-benzamido] 4 (p-methoxyphenylazo) -5-pyrazolone,9.N (4 benzoylacetaminobenzeuesulfonyl) N (yphenyl-propyl)-p-toluidine(U. S. Patent 2,298,443) 10.

amylphenoxy) n butyramido] 7 acetanilide (Mc- Crossen U. S. applicationSerial No. 295,806, riow' U. S. Patent 2,728,658, issued December 27,1955) ot-{3-[oc-(2,4-di tert. amylphenoxy)acetamido]henzoyl}-2-methoxyacetanilide p 3 benzoylacetamido-4-methoxy 2',4 ditertfamyl- Phenoxy acetanilide i i a-o-methoxylbenzoyl-a-chlorol-[a (2,4di tert.

9, 13 4-benzoylacetamido-3-methoxy-2',4' di tert. amylcompounds ofFormula H, in addition to their super phenoxy acetanilide i 1sensitizing effect, have an antistaining and antifog gant Theaccompanying drawing illustrates the supersem efiect in certainemulsions containing color couplers, such sitizing eflFect obtained withthree of our new combinaas if ei i p eg F 1 1 tions ingelatino-silver-chlorobromide emulsions. Each e omc acl s of a H aregenerally figure of the drawing is a diagrammatictreproduction of ployedm neutral aqueous solutlen mentloned above two spectrograms. Thesensitivity of the emulsion C011? the free acids are at P partiallyneutralized with taining only the neopentylene dye represented by For-Sodmm hydroxide Potasslun} hydroxlde Sodmni mula I is represented by thesolid line, while the bonate, ammonia, triethylamine, etc. before, usein the Sitivity of the same emulsion containing both a emulsions. Thecorresponding disulfonic acid salts repentylene dye of Formula I and thetriazine compound mm It thus Poeslble to adlust the PH of these ofFormula II is represented by the broken line. No one Solutions that theyare about the e as the curve for the emulsion containing the triazinecompound PH of the emulslonsof Formula II alone is given, since it hasbeen found What we claim as inventiol} and desire Secured that thesecompounds alone generally have little or no Letters Patent of the Un1ted States 153 measurable sensitizing eifect on the emulsions. Aphotograpillq sliver hallde \imulslQn sensltlzed In Fig. 1, curve Arepresents the sensitivity of an with a supersensltizlng combination ofat least one ordinary gelatino-silver-chlorobromide emulsioncontaincyanine dye selected from the class represented by the ing 3,3diethyl 9,11 neopentylenethiadicarbocyanine following general formula:

R: R: X a //Z\\ H2O CH: z, a-t r==oon=o o-oH =oH-on s.l=6( :on=om,iiwnlI y I t a X 0 H iodide, while curve B represents the sensitivity of thewherein R and- R each represents an alkyl group consame emulsionsensitized with 3,3'-diethyl-9,11-neopent taining from 1 to 4 carbonatoms, R and R each repreylenethiadicarbocyanine iodide and 4,4-bis(4-phenoxysents a member selected from the group consisting of a 6 3hydroxyethylamino s triazin 2 ylamino)- hydrogen atom and a methylgroup, X represents an stilbene-2,2'-disulfonic acid, acid radical, drepresents a positive integer of from 1 to In Fig. 2, curve C representsthe sensitivity of an ordi- 3, n represents a positive integer of fromlto 2, Z reprenary gelatino-silver-chlorobromide emulsion sensitizedsents the non-metallic atoms necessary to complete a ith 3,3 diethyl9,11 neopgmylene 6,7,6'7' di heteroeyclic nucleus selected from thegroup consisting of benz'othiatricarbocyanine iodide, while curve Breprethose of the benzothiazole series and those of the naphsents thesensitivity of the same emulsion sensitized with thothiazole series, andZ represents the non-metallic 3,3 diethyl 9,11 neopentylene 6,7,67dibenzoatoms necessary to complete a heterocyclic nucleussethiatricarbocyanine iodide and 4,4'-bis(4-phenoxy-6-fi-hylected fromthe group consisting of those of thebenzodroxyethylamino s triazin 2ylamino) stilbene -2,2- thiazole series, those of the naphthothiazoleseries, those di ulfo ic id, of the benzoxazole series, those of thenaphthoxazole In Fig. 3, curve B represents the sensitivity of anordiseries, those of the benzoselenazole series, those of the narygelatino-silver-chlorobromide emulsion containing naphthoselenazoleseries, those of the 2-quinoline series, 3,3 diethyl 9,11neopentylenethiatricarbocyanine those of the 4-quinoline series, thoseof the benzimidazole iodide, while curve F represents the sensitivity ofthe series, and those of the benzoquinoline series, and at least sameemulsion sensitized with 3,3' diethyl-9,11-neoonebis-(s-triazin-2-ylamino)stilbene compound selectedpentylenethiatricarbocyanine iodide and 4,4-bis(4-phenfrom the classrepresented by the following general oxy 6 p hydroxyethylamino striazin- 2 ylformula: 1 a i amino)stilbene-2,2'-disulfonic acid.

Sensitometric measurements for. coatings similar to N inf TNH NE Y thoseshown in Figs. 1,2 and 3 are given in Examples 3, 1 N CH=OH L 4and5,respectively, of Tablelabove. p

By ,bis(s triazin, 2 ylamino)stilbene, compound,

wemean a compound of thefollowing structuref R1 p wherein R R R and Reach represents a member D-NH N 1" selected from the group consisting ofa hydrogen atom, 03:93 a hydroxyl group, an aryloxy group, an alkoxylgroup, Q t a halogen atom, a heterocyclic; radical, analkylthio 4 group,an arylthio group, andan amino group, and R and R each represents amember selected fromthe wherein R and R each have the values given abovegroup;consisting of a hydrogen atomand a. sulfo group. andiD and D eachrepresents a s-triazin-Z-yl nucleus. 2.;A photographic 'gelatino-silverhalide developing- We have also found that the triazine compound of outemulsion sensitized with at least one cyanine dye 'se Formula II abovewherein Rfi, R R5 and/or' R each lected from the class represented by'the following genrepresents a heterocyclyamino' group '(e. g.,2-benzoeral formula: 1

thiazylamino, Z-pyridyIamino,etc.) can alsobe used to wherein R and Reach represents an alkyl group conadvantage in our invention. We havefound'also that the taining from 1 to 2 carbon atoms,d represents apositive integer of from 1 to 3,.n represents a positive integer of from1 to 2', X represents an acid radical, Z represents the non-metallicatoms necessary to complete a heterocyclic nucleus selected from thegroup consisting of those of the benzothiazole series and those of thenaphthothiazole series, and Z represents the non-metallic atomsnecessary to complete a heterocyclic nucleus selected from the groupconsisting of those of the benzothiazole series, those of thenaphthothiazole series, those of the benzoxazole series, those of thenaphthoxazole series, those of the benzoselenazole series, those of thenaphthoselenazole series, those of the 2-quinoline series, those of the4-'quinoline series, those of the benzimidazole series, and those of thebenzoquinoline series, and at least one bis(s-triazin-2-ylamino)stilbenecompound selected from the class represented by the following generalformula:

D-NHQorhoH wherein R and R each represents an alkyl group containingfrom 1 to 2 carbon atoms, X represents an acidradical, d represents apositive integer of from 1 to 3, and Z represents the non-metallic atomsnecessary to complete a heterocyclic nucleus of the benzothiazoleseries, and at leastone bis(s-triazin-2-ylamino)stilbene compoundselected from the class represented by the following general formula:

l R4 R5 wherein R R R and R each represents a member selected from thegroup consisting of a hydrogen atom,

a hydroxyl group, an aryloxy group, an alkoxyl group,

a halogen atom, a heterocyclic radical, an alkylthio group, an arylthiogroup, and an amino group and R 'andR each represents a member selectedfrom the group consisting'of a hydrogen atom and a sulfo group.

6. A photographic gelatino-silver-halide emulsion sen sitized with asupersensitizing combination of a cyanine dye selected from the classrepresented by the following 1 general formula:

wherein R and R each represents an alkyl group containing from 1 to 2carbon atoms, X represents an acid radical, d represents a positiveinteger of from 1 to 3, and Z represents the non-metallic atomsnecessary to complete a heterocyclic nucleus of the benzothiazoleseries, and at least one bis(s-triazin-Z-ylamino)stilbene compoundselected from the class represented by the following general formula:

DNH-

SOaH SOQH wherein D and D each represents a s-triazin-2-yl nucleus. 7. Aphotographic gelatino-silver-halide developing-out emulsion sensitizedwith a supersensitizing combination of a3,3-diethy1-9,11-neopentylenethiatetracarbocyanine salt and at least onebis(s-triazin-Z-ylamino)sti'lbene compound selected from the classrepresented by the following formula:

wherein D and D each represents a s-triazin-Z-yl nucleus. 8. Aphotographic gelatino-silver-halide developing-out emulsion sensitizedwith a supersensitizing combination of 3,3 diethyl 9,11neopentylenethiatetracarbocyanine iodide and4,4-bis[4-(4-sufoanilino)-6-[3-hydroxyethylamino s triazin 2 ylamino]stilbene 2,2 disulfonic acid. 9. A photographic gelatino-silver-halidedeveloping-out emulsion sensitized with a supersensitizing combinationof a 3,3 diethyl 9,11 neopentylenethiadicarbocyanine salt and atleastone bis(s-triazin-Z-ylamino)stilbene compound selected from theclass represented by the following formula:

NH-D 1 wherein D and D each represents a s-triazin-Z-yl nucleus. 1 Y 12.A photographic: gelatino-silver-halide' developing out emulsionsensitized With a supersensitizing'combination of3,3-diethyl-.9,1l-neopentylenethiatricarbocyanine iodide and 4,4-bis[4-phenoXy-6- (fl-hydroxyethylamino) s-triazin-Z-ylamino]stilbene-2,2-disulfonic acid.

13. A photographic gelatino-silver-halide developingout emulsionsensitized with a supersensitizing combination of3,3-diethyl-9,1l-neopentylenethiatetracarbocyanine iodide and4,4'-bis[4-phenoxy-6-(B-hydroxyethylamino) -s-triazin-2-ylamino]-stilbene-2,2'-disulfonic acid.

14.5A photographic gelatino-silver-halide. emulsion sensitized with 3:1supersen'sitiz'ing, combination of. a cya nine dye selected from theclass represented by the following general formula:

wherein R and R each represents an alkyl group containing from 1 to 2carbon atoms, X represents an acid radical, d represents a positiveinteger of from 1 to 3, and Z represents the non-metallic atomsnecessary to complete a heterocyclic nucleus of the naphthothiazoleseries, and at least one bis(s-triazin-2-ylamino)stilbene compoundselected from the class represented by the following general formula:

N N 3 RT NNH OH=GH NH IL In wherein R and R each represents an alkylgroup containing from 1 to 2 carbon atoms, X represents an acid radical,d represents a positive integer of from 1 to 3, and Z represents thenon-metallic atoms necessary to complete a heterocyclic nucleus of thenaphthothiazole series, and at least onebis(s-triazin-2-ylamino)stilbene compound selected from the classrepresented by the following general formula:

wherein D and D each represents a s-triazin-2-y1 nucleus.

16. A photographic gelatino-silver-halide developingout emulsionsensitized with a supersensitizing combination of a3,3'-diethyl-9,11-neopenty1ene-6,7,6,7'-dibenzothiatricarbocyanine saltand at least one bis(s-triam'n- 2-ylamino)stilbene compound selectedfrom the class represented by the following general formula:

NH-Dg SOsH 805E wherein D and D each represents a s-triazin-Z-ylnucleus.

17. A photographic gelatino-silver-halide developingout emulsionsensitized with a supersensitizing combination of3,3'-diethyl-9,11-neopentylene-6,7,6',7'-dibenzothiatricarbocyanineiodide and 4,4'-bis[4-phenoxy-6-(flhydroxyethylamino) s triazin 2ylaminolstilbene- 2,2'-disnlfonic acid.

References Cited in the file of this patent UNITED STATES PATENTS2,367,551 Yule Jan. 16, 1945 2,476,536 Dersch July 19, 1949 2,718,466Wolfson Sept. 20, 1955 2,734,900 Heseltine Feb. 14, 1956

